JP7241487B2 - Polyurethane based manufacturing - Google Patents

Description

The present invention relates to the field of polyurethanes, in particular in the presence of one or more catalysts for the isocyanate-polyol and/or isocyanate-water reaction and/or isocyanate trimerization of at least one polyol component with at least one isocyanate component. wherein said reaction is carried out in the presence of a carrier material and polyamine P, said carrier material used being, for example, fumed silica, and It relates to a polyurethane system thus obtained.

Polyurethane systems targeted by the present invention are, for example, polyurethane paints, polyurethane adhesives, polyurethane sealants, polyurethane elastomers or, in particular, polyurethane foams.

Polyurethanes have excellent mechanical and physical properties and are therefore used in a very wide variety of fields. The foam sector includes a variety of polyurethanes, such as conventional flexible foams based on ether and ester polyols, low temperature cure foams (often also referred to as HR foams), rigid foams, integral foams, and microcellular foams; There is also a particularly important market for foams with properties in between these classes, such as semi-rigid systems. For example, rigid foams are used as interior roof liners, ester foams are used as door trims and in die-cut sun visors, and cold cure foams and flexible foams are used in seating systems and mattresses. Adhesives and paints are another area where polyurethanes are used, where they are of interest due to their superior properties.

Polyurethane foam releases aldehydes during manufacturing and storage. Due to health concerns, however unfounded, many consumers seek to avoid using aldehyde-emitting products.

Moreover, in recent years, Chinese government authorities have become particularly demanding, imposing strict limits on emissions in the interior of automobiles sold in China. There the focus is again on aldehydes as well as aromatic hydrocarbons. Thus, polyurethane foams with the lowest possible level of aldehyde generation are generally desired.

Various methods have already been tried to meet this demand. For example, in WO 2009/117479, it is assumed that formaldehyde is generated from the raw material, more specifically, it is assumed that formaldehyde is contained in the amine catalyst (tertiary amine) used. there is The publication proposes to reduce formaldehyde emissions by adding a primary amine to the tertiary amine catalyst. Preference is given to using dimethylaminopropylamine.

DE 10003156 A1 does not directly relate to low-emission foams, but addresses the problem of developing polymers with very good adsorption capacity for various compounds, especially for heavy metal ions. Proposed solutions to this problem include polyurethanes containing ethyleneimine, polyethyleneimine, polyvinylamine, carboxymethylated polyethyleneimine, phosphonomethylated polyethyleneimine, quaternized polyethyleneimine, and/or dithiocarbaminated polyethyleneimine. It takes the form of a form. These polyurethane foams are also useful for adsorbing organics such as formaldehyde.

DE 102 58 046 A1 addresses the problem of producing polyurethane foams with reduced formaldehyde emission levels. In contrast to DE 10003156, the problem addressed by DE 10258046 was thus to reduce formaldehyde emissions from polyurethane (PU) foams as such. and does not adsorb formaldehyde from ambient air. A proposed solution to this problem is a process comprising mixing the amino-containing polymer into the polyurethane foam, said mixing being carried out before and/or during the production of the polyurethane foam.

However, in the context of the present invention, it has been found that the use of aldehyde scavenging materials can cause foam defects and, in some circumstances, affect the efficacy of absorbing aldehydes, depending on the formulation of the polyurethane used. bottom. The use of aldehyde scavengers known from the prior art can under some circumstances inhibit the processability of the foam and also reduce the compressibility of the foam, i.e. the "force-to-crush". (FTC) values are likely to drop in particular.

Suppliers of polyurethanes, particularly polyurethane foams, therefore, still need further solutions to reduce aldehyde emissions without loss of processability or mechanical properties.

Against this background, the particular problem addressed by the present invention is to provide polyurethanes, in particular polyurethane foams, with reduced levels of aldehyde emissions and improved processability, in particular the compressibility of the foams. , to maintain better in terms of "force-to-crush" (abbreviated FTC) values.

The inventors have now surprisingly found that the preparation of the polyurethane system in the presence of a carrier material and a polyamine P can solve this problem.

Accordingly, the present invention provides for the reaction of at least one polyol component with at least one isocyanate component in the presence of one or more catalysts for isocyanate-polyol and/or isocyanate-water reactions and/or trimerization of isocyanates. The subject of the subject matter is a method for producing a polyurethane system by allowing the reaction to be carried out in the presence of a carrier material and a polyamine P.

Preferably, the carrier material is a powder. The support material used is in particular fumed silica or precipitated silica, which advantageously has a primary particle size, in particular in the range from 5 nm to 100 nm, and a BET specific surface area, in particular from 30 m ² /g to 800 m ^{2 .} /g.

It should be noted that there are good reasons for those skilled in the art, based on the known prior art, to omit the use of carrier materials, which are generally considered to hinder PU foam production. because there is According to the prior art, this is especially true for polyethyleneamines applied to silica.

Contrary to this general opinion, what is important in the present invention is specifically the presence of a support material, especially fumed silica or precipitated silica.

The subject of the present invention is to reduce aldehyde emissions compared to the use of aldehyde scavengers according to the prior art and to improve processability, especially compressibility, or "force-to-crush" (FTC for short). It makes it possible to provide polyurethanes, in particular polyurethane foams, which are improved in terms of value. More specifically, compared to common methods, the compressibility can be stabilized well without the use of additives, resulting in a difference of less than 30%. Form defects can be avoided.

In the context of the present invention, "polyamine P" is a polyamine having a molecular weight of at least 100 g/mol and having at least two primary or secondary amino groups per molecule, in particular a polyamine having a molecular weight of at least 200 g/mol. and having at least three primary or secondary amino groups per molecule.

If the polyamine P has a molar mass distribution, its molecular weight in the context of the present invention is in each case the number average molecular weight. The number average molecular weight can be obtained, in particular, by GPC measurement in terms of polystyrene.

In a preferred embodiment, the polyamine P has a number average molecular weight of at least 500 g/mol, preferably at least 1,000 g/mol, more preferably at least 1,500 g/mol, particularly preferably at least 2,000 g/mol, especially at least 2 , 500 g/mol. Although the upper limit of the number average molecular weight is not generally limited, it is preferably 1,000,000 g/mol or less, more preferably 750,000 g/mol or less.

In a preferred embodiment, the polyamine P has an amino functionality of at least 4, preferably at least 5 and more preferably at least 6 per molecule. The upper limit of amino functionality is generally not limited, but preferably 10 or less.

In the context of the present invention, particularly preferred polyamines P have the formula (I) H ₂ N--CH ₂ --CH ₂ --NH--(CH ₂ --CH ₂ --NH) _x --CH ₂ --CH ₂ --NH ₂ , in which x=0 to 4, preferably 1 to 3, especially 1, and reaction products thereof, especially with guanidine salts. In the context of the present invention, said reaction products are also referred to as guanidine adducts and are particularly preferred polyamines P.

In the context of the present invention, further preferred polyamines P are the amines described as aldehyde scavengers in WO2016201615A1, preferably amines having at least one 1,3-propanediamino function, such as More specifically, N,N'-dimethylpropanediamine, N',N'-diphenylpropanediamine, 1-benzyl-1,3-propanediamine, isotridecyloxypropyl-1,3-diaminopropane, dodecyloxy Propyl-1,3-diaminopropane and hexyloxypropyl-1,3-diaminopropane, most preferably isotridecyloxypropyl-1,3-diaminopropane. The use of these polyamines P is a particularly preferred embodiment within the meaning of the invention.

Further preferred polyamines P in the context of the present invention are reaction products of unsaturated nitriles with aliphatic polyamines having at least two or more amine groups, preferably three or more amine groups. The unsaturated nitrile used is in particular 2-propenenitrile and the aliphatic polyamine used is in particular diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine and/or hexa Particularly preferred is methylenediamine, the reaction product of 2-propenenitrile and diethylenetriamine. In one particularly preferred embodiment in the sense of the invention, these polyamines P are used.

According to the invention, in the presence of carrier material and polyamine P, a polyurethane system is produced. For the purposes of the present invention, this means using a polyamine P, eg a guanidine adduct, together with a carrier material. More specifically, polyamine P is applied to the carrier material.

For the effect desired according to the invention in polyurethane foams, in particular
(i) the polyamine P and the carrier material are added separately to the reaction mixture used to prepare the polyurethane system, said carrier material preferably being dispersed in the liquid,
(ii) it is possible to mix the polyamine P with the carrier material prior to addition to the reaction mixture used to prepare the polyurethane system;

In this case, the mixing according to (ii) is preferably carried out by dispersing the carrier material in a liquid and mixing this dispersion with the polyamine P (corresponding to iia).

Furthermore, the mixing according to (ii) involves directly mixing the carrier material in powder form with the polyamine P (corresponding to iib), preferably a dispersion comprising the polyamine P as the continuous phase and the carrier material as the dispersed phase. It is preferably performed as it is produced.

Further, according to the mixing in (ii), the polyamine P can be adsorbed onto the carrier material.

What is important in the context of the invention is in each case the combined use of carrier material and polyamine P, ie the polyurethane system is produced in the presence of carrier material and polyamine P.

The subject of the invention is to solve the problem addressed by the invention. Thus, whenever the process for producing a polyurethane system is carried out in the presence of a carrier material and polyamine P, it is possible to provide polyurethanes, in particular polyurethane foams, with reduced aldehyde emissions, while at the same time thereby: The processability of the foam is improved compared to standard processes without additives. More specifically, the compression characteristics (FTC) are preferably only slightly adversely affected, with a maximum difference of 30%. Form defects are kept to a minimum.

Relative to the polyol system, the absolute amount of carrier material is in particular in the range from 0.001 wt.

Support materials that can be used according to the invention include, in particular, synthetic silica. They are generally distinguished by their method of preparation into fumed silica, especially prepared by the AEROSIL method by flame hydrolysis or high temperature hydrolysis, and precipitated silica, especially synthesized by the wet method.

The AEROSIL process can essentially be described as continuous flame hydrolysis of silicon tetrachloride ( _SiCl4 ). In this case SiCl ₄ is converted to the gas phase and then reacts spontaneously and quantitatively with hydrogen formed as an intermediate in a hydrogen/oxygen gas flame to form the desired silicon dioxide and HCl gases. . Concentration of co-reactants (e.g. SiHCl ₃ , H ₃ SiCl, otherwise called exothermic special oxides such as AlCl ₃ , TiCl ₄ , ZrCl ₄ ), flame temperature, and retention of silica in the combustion space. By varying the time, it is possible to influence the particle size, particle size distribution, specific surface area, and surface properties of silica within wide limits. Special oxides such as TiO ₂ and Al ₂ O ₃ are distinguished here by being available in crystalline form, in contrast to silicon dioxide, which is completely amorphous. An "amorphous" material is a material whose atoms do not form any ordered structures, form irregular patterns, and have only short-range order and no long-range order. The short residence time in the hydrogen/oxygen gas flame virtually excludes the sintering process between the condensed phases. If the material has not yet left the factory, it is particularly susceptible to reaction with silanes in further processing. For example, silica, a substantially hydrophilic starting material, can be effectively and homogeneously functionalized by chemical post-treatment in a continuous process, so that the silica subsequently becomes a hydrophobic surface. have characteristics. Aerosil surface functionalization is performed with halosilanes, alkoxysilanes, silazanes, and siloxanes. With this improvement, the post-treated silica exhibits new and important performance.

On the other hand, precipitated silica is produced from water glass solution, to which sulfuric acid is added under certain conditions. Thus, precipitated silica is formed in the aqueous phase. Precipitation conditions can produce silica with smaller or larger primary particles than the product produced, which substantially determines the size of the specific surface area. The precipitate thus obtained is washed and dried by various methods (rotary drying, spray drying). The observed particle size of agglomerated silica is preferably in the range of 50 μm to 150 μm. Then, depending on the drying method employed, the silica can or must be ground. Grinding significantly reduces the particle size, but does not affect the size of the specific surface area.

Silica is characterized in particular in terms of its specific surface area (according to the BET (Brunnauer, Emmett and Teller) formula according to DIN 66131) and the size of the primary particles. Specifically, in the case of Aerosil, it is generally difficult to specify the particle size because the primary particles are generally integrated into agglomerates at various levels of size.

More particularly, in the context of the present invention, the polyamines P used may all be guanidine reaction products, said reaction products being obtained by reacting guanidine salts with polyamines, said polyamines containing Also included are, in principle, polyamines with higher molar masses, for example >500 g/mol, >1,000 g/mol or >2,000 g/mol.

The present invention ensures that aldehyde emissions are minimized even during long-term storage. In fact, acetaldehyde emission levels are adversely affected to a significant level, if at all, as the use of, for example, PEI prevents significant increases in acetaldehyde emission levels during storage. and at least not to the extent that the acetaldehyde content of the polyurethane foam is significantly increased, for example by a factor of 50, as is the case with the use of PEI. Thus, the rise in acetaldehyde emissions during storage is clearly reduced to a minimum. More specifically, even after a storage period of 5 months, the increase in acetaldehyde content of the polyurethane foam is no more than 2.5 times compared to the foam without additives to reduce formaldehyde emissions. , which is advantageous. This is a significant improvement over prior art proposals involving the use of PEI.

More particularly, the present invention is directed to already manufactured polyurethane systems (especially polyurethane Formaldehyde emissions from foams) are reliably reduced, preferably to values below 0.02 mg of formaldehyde per kg of PU system (PU foams).

The process according to the invention thus makes it possible to provide polyurethane systems (especially polyurethane foams) which give very good results not only with regard to aldehyde emissions, but also with respect to processability. By combining and mixing the carrier material and the polyamine P according to the invention, it is possible to provide polyurethane systems, in particular polyurethane foams, in which the aldehyde emissions are reduced and the acetaldehyde emissions are adversely affected. and, preferably, relatively rare aldehydes such as benzaldehyde or acrolein can also be absorbed.

A further advantage of the present invention is that the polyurethane systems obtained have a biocidal effect or have a biocidal effect that is higher than that of conventional polyurethane systems. A further advantage of the present invention is that the process of the present invention accelerates the reaction of the reactants compared to processes that do not use a carrier material and polyamine P in combination.

The compounds used in the present invention, their method of preparation, the use of the compounds for making polyurethane systems/foams, the use of the compounds for making polyurethane systems/foams, and the polyurethane systems/foams themselves are given by way of example. Although described below, the invention is not limited to these exemplary embodiments. Where ranges, general formulas, or classes of compounds are specified below, these exclude individual values (ranges) for the compounds, as well as the respective ranges or groups of compounds specifically described. It also includes all subregions and subgroups of compounds obtained by Where a document is cited within the context of this specification, its content, particularly regarding the subject matter referenced, is considered to be included in the disclosure content of the present invention in its entirety. Percentages are by weight unless otherwise stated. Unless otherwise stated, the averages referred to below are weight averages. When material properties, such as viscosity, are referred to below, they relate to the material properties at 25° C. unless otherwise stated. When chemical (empirical) formulas are used in the present invention, values reported may be average values as well as absolute numbers. Values for polymeric compounds are preferably average values.

In the context of the present invention, carrier material and polyamine P are used. Preferred polyamines P are reaction products of guanidine salts and polyamines. The reaction of guanidine salts with polyamines, especially compounds of formula (I), may be carried out as described in the prior art. Guanidine reaction products are well known to those skilled in the art. GB-A-657753 describes two possible methods for synthesizing derivatives of guanidine reaction products and guanidine salts. One method for obtaining the guanidine reaction product is by reacting an amine compound, such as diethylenetriamine, with a guanidine salt, such as guanidine carbonate, to obtain the salt form of the product. Another way to obtain this class of compounds is to react an amine with cyanamide or dicyandiamide and then treat the product with an organic or inorganic acid to convert the treated product to its corresponding salt. The method. The resulting product is also a guanidine reaction product within the meaning of the present invention. The reaction can also be carried out directly in the presence of an acid, as described in EP-A-2300418, in which case the product is the corresponding salt of the alkylguanidine compound. Alternatively, the amine salt may be converted to biguanidine by reaction with dicyanamide or sodium dicyanamide. A further suitable set of synthetic methods is described in Ullmann's Encyclopedia of Industrial Chemistry "Guanidine and Derivatives" and in a review by Katritzky et al. (Journal of Organic Chemistry, 2010, p.76).

Guanidine reaction products which can preferably be used for the purposes of the present invention are guanidine salts, in particular guanidine acid addition salts, and polyamines, preferably at temperatures of from 90° C. to 150° C., preferably at reaction times of from 5 to 36 hours. It can be obtained in an advantageous manner by reacting, in which case the ammonia formed may optionally be removed from the reaction mixture using a vacuum pump. The use of a suitable solvent can be advantageous, as the viscosity of the reaction mixture can increase considerably as the reaction progresses. Additionally, after the reaction is complete, the water and product can be mixed. Depending on the viscosity of the product, the mixing may be carried out at room temperature or at a higher temperature.

guanidine salt and polyamine, especially the compound represented by formula (I), at a molar ratio of 5:1 to 1:5, preferably 1:1 to 1:3, especially 2:3 to 1:3; The reaction is carried out with polyamines, in particular compounds of formula (I). A molar ratio of guanidine salt to polyamine of 1:3, 1:2 or 2:3 is particularly preferred.

Optionally, depending on the system into which the guanidine reaction product is subsequently incorporated, in subsequent steps properties such as viscosity, solubility, polarity, and miscibility are as appropriate to the system as possible. Additionally, it is advantageous to at least partially react the reaction product with a functionalizing agent. Useful functionalizing agents include, among others, polymeric or monomeric components having functional groups capable of reacting with amino groups, such as epoxides, acids, alkyl halides, dialkyl sulfates, and the like. This procedure is known per se to those skilled in the art who can routinely carry out any functionalization with some field trials if necessary. Thus, the concept of guanidine reaction products also includes functionalized guanidine reaction products.

A guanidine reaction product that can be used for the purposes of the present invention can be converted to the corresponding basic guanidine derivative by mixing with a base such as sodium ethoxide, said basic guanidine derivative Due to its strong basicity, it can act as a catalyst to produce PU systems. Here we also deal with guanidine reaction products that can be used for the purposes of the present invention.

In principle, any known guanidine salt can be reacted in the present invention, such as preferably guanidine hydrochloride, guanidine sulfamate, guanidine phosphate, guanidine acetate, guanidine carbonate, guanidine sulfate, thiocyanate guanidine acid, guanidine nitrate, and the like. In particular guanidine hydrochloride and/or guanidine carbonate can be used as guanidine salts. Products resulting in a similar manner from the reaction of biguanidine with polyamines are also guanidine reaction products within the meaning of the present invention.

Further, the original counterion of the derivatized guanidine salt (i.e., the original counterion of the guanidine reaction product) can be converted to other counterions by an ion exchanger, as known to those skilled in the art, for example, from WO2008080184. can be replaced with

A particularly preferred guanidine reaction product for use in the present invention is represented by formula (II)
H[—(HN—CH ₂ —CH ₂ ) _a —NH—C(=NHR ⁺ X ⁻ )] _c —NH—(CH ₂ —CH ₂ —NH—) _b H (II)
is a compound represented by
Said compound is obtained by reacting a guanidine salt with a compound of formula (I), wherein
a is independently 0 to 6, advantageously 2 to 6, preferably 3 to 5, especially 3 or 4,
b is independently 0 to 6, advantageously 2 to 6, preferably 3 to 5, especially 3 or 4;
c is independently 1 to 4, preferably 1 or 2, preferably 1,
R is independently H or (CH ₂ —CH ₂ —NH—) _d H, especially H;
d is independently 0 to 6, advantageously 2 to 6, preferably 3 to 5, especially 3 or 4;
If d>0 and R is not H, a and b may each be 0; if a>0, d and b may each be 0; or if b>0, d and each a may be 0,
X ⁻ is an anion, preferably a halide, especially chloride.

CO ₃ ^2- may function as an anion.

In preferred compounds of formula (II), a=b and a=b=2 to 6, preferably 3 to 5, especially 3 or 4, more preferably 3, X ⁻ is preferably chloride, R is preferably H and c=1 or 2 is preferred. These compounds are obtainable in particular by reacting guanidine salts with polyamines of the formula (I).

Therefore, in a preferred embodiment of the method according to the invention, formula (II)
H[—(HN—CH ₂ —CH ₂ ) _a —NH—C(=NHR ⁺ X ⁻ )] _c —NH—(CH ₂ —CH ₂ —NH—) _b H (II)
Carrying out the reaction in the presence of a compound represented by
Said compound is obtained by reacting a guanidine salt with a compound of formula (I), wherein
a is independently 0 to 6, advantageously 2 to 6, preferably 3 to 5, especially 3 or 4,
b is independently 0 to 6, advantageously 2 to 6, preferably 3 to 5, especially 3 or 4;
c is independently 1 to 4, preferably 1 or 2, preferably 1,
R is independently H or (CH ₂ —CH ₂ —NH—) _d H, especially H;
d is independently 0 to 6, advantageously 2 to 6, preferably 3 to 5, especially 3 or 4;
if d>0 and R is not H, a and b may each be 0; if a>0, d and b may each be 0; or if b>0 , d and a may each be 0,
X ⁻ is an anion, preferably a halide, especially chloride.

In preferred compounds of formula (II), in compounds of formula (II) a=b and a=b=2 to 6, preferably 3 to 5, especially 3 or 4, More preferably 3, X ⁻ is preferably chloride, R is preferably H and c=1 or 2 is preferred.

Formula (III) below shows an example of a compound represented by formula (II), wherein X ⁻ is Cl ⁻ , a=b=3, c=2, and R is H. be.

In a particularly preferred embodiment of the invention, the proportion of compounds of formula (II) in which a=b=2 to 6, especially 3 or 4, in the process of the invention is 40 wt % or more of the compound obtained by reacting the guanidine salt with the compound of formula (I). The ratio of the compound of formula (II), where a=b=2 to 6, especially 3 or 4, is the ratio of the compound of formula (I) to the guanidine salt. It is preferably 60 wt % to 80 wt %, particularly 90 wt % to 98 wt % of the compound obtained by the reaction.

In one preferred embodiment of the invention, not only the guanidine reaction product is added, but also at least one aliphatic polyamine with a molar mass of preferably less than 400 g/mol, advantageously less than 300 g/mol, especially 250 g/mol. In addition, said aliphatic polyamines are advantageously aliphatic polyamines containing at least two or more amino groups, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, hexamethylene. diamine, 1,8-diaminotriethylene glycol, tris(2-aminoethyl)amine. Furthermore, the optionally used aliphatic polyamine is used in an amount of, for example, 0.001 wt% to 10 wt%, preferably 0.01 wt% to 5 wt%, especially 0.05 wt% to 3 wt%, relative to the polyol component. You may This is understood as an additional amount relative to the polyamine P which is not critical.

The guanidine reaction product for the purposes of the invention, ie the preferred polyamine P according to the invention, may be formed in situ. That is, guanidine reaction products are formed only during the reaction of the polyol component with the at least one isocyanate component, particularly in the preparation of polyurethane systems from suitable reactants of guanidine salts and polyamines. Thus, in other words, the process of the invention also provides the possibility of forming a guanidine reaction product, namely the preferred polyamine P according to the invention, only in the reaction mixture for producing the polyurethane system. include. This corresponds to a preferred embodiment of the invention. However, it is more preferred to use pre-synthesized guanidine reaction products to prepare the polyurethane system.

Polyurethane systems may also be produced in another conventional manner, as described in the prior art. This is well known to those skilled in the art. General summaries can be found, for example, in Hanser/Gardner Publications Inc. (Cincinnati, Ohio) published by G.I. Oertel, Polyurethane Handbook, 2nd edition, 1994, pages 177-247. In the process for preparing the polyurethane system according to the invention, the polyamine P, preferably the guanidine reaction product, is added in an amount of 0.01 to 20 parts, preferably 0.05 to 5 parts, especially 0.05 part to 100 parts of the polyol component. It is preferred to use a mass fraction of 1 to 3 parts.

It may be advantageous to carry out the method for producing a polyurethane system according to the invention and additionally to mix water, physical blowing agents, flame retardants and/or further additives.

Any isocyanate may be used as the isocyanate component in the process of the present invention, said isocyanates being in particular polyfunctional aliphatic, cycloaliphatic and araliphatic polyfunctional isocyanates known per se. , and preferably aromatic polyfunctional isocyanates. Suitable isocyanates for the purposes of the present invention include, for example, any polyfunctional organic isocyanate such as 4,4′-diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI), and isophorone diisocyanate ( IPDI). The various TDI isomers in pure form or as mixtures of isomers, as well as the more highly enriched TDI isomers, known as MDI and crude MDI (“polymeric MDI”), have an average functionality of 2-4. Mixtures with similar analogues are particularly preferred. A mixture of TDI and MDI is a particularly preferred isocyanate.

All organics having two or more isocyanate-reactive groups, and preparations thereof, are preferably polyols suitable as the polyol component for the purposes of the present invention. Suitable polyols are all polyether polyols and polyester polyols commonly used for producing polyurethane systems, especially polyurethane foams. It is preferred that the polyol is not a compound having one or more five- or six-membered rings composed of one or two oxygen atoms and carbon atoms.

Polyether polyols may be obtained by reacting polyfunctional alcohols or amines with alkylene oxides. Polyester polyols are esters of polybasic carboxylic acids (which can be aliphatic, for example adipic acid, or aromatic, for example phthalic acid or terephthalic acid), with polyhydric alcohols (usually glycols). is preferably included as a main component. Natural oil-based polyols (NOPs) can also be used. These polyols are derived from natural oils such as soybean oil or palm oil and can be used in modified or unmodified form.

A further class of polyols are those obtained as prepolymers resulting from the reaction of polyols with isocyanates in molar ratios of 100:1 to 5:1, preferably 50:1 to 10:1.

Another further class of polyols that can preferably be used are so-called filled polyols (polymer polyols). They contain dispersed solid organic fillers with a solids content of 40% or more. Among these, for example, those described below may be used.
SAN Polyol: A highly reactive polyol containing dispersed copolymers based on styrene-acrylonitrile (SAN).
PHD Polyol: A highly reactive polyol containing polyurea in a similarly dispersed form.
PIPA Polyols: Highly reactive polyols containing dispersed polyurethanes, such as those formed by the in situ reaction of isocyanates and alkanolamines in conventional polyols.

The solids content, which is preferably in the range of 5 wt% to less than 40 wt% relative to the polyol depending on the application, plays a role in improving cell opening, thereby forming the polyol in a controlled manner, especially with TDI. and no foam shrinkage occurs. As such, the solids serve as important processing aids. A further function is to control the hardness by solids content, since a higher solids content will result in a portion of the foam having a higher hardness.

Formulations containing solids-containing polyols are significantly less self-stabilizing and tend to require physical stabilization in addition to chemical stabilization via cross-linking reactions.

Depending on the solids content of the polyol, these are used alone or mixed with the unfilled polyols described above.

Preferred ratios of isocyanate component to polyol component for the purposes of the present invention, expressed as indices, are in the range 10-1000, preferably 40-350. This index indicates the ratio of the isocyanate actually used and the isocyanate calculated for the stoichiometric reaction with the polyol. An index of 100 represents a 1:1 molar ratio of reactive groups.

Suitable catalysts that can be used in the process of the present invention are preferably substances that catalyze the isocyanate gel reaction (isocyanate-polyol), the isocyanate foam reaction (isocyanate-water), or the isocyanate dimerization or trimerization. . Representative examples include triethylamine, dimethylcyclohexylamine, tetramethylethylenediamine, tetramethylhexanediamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenediamine, dimethylpiperazine, 1,2-dimethylimidazole, N-ethylmorpholine, tris Amines such as (dimethylaminopropyl)hexahydro-1,3,5-triazine, dimethylaminoethanol, dimethylaminoethoxyethanol, and bis(dimethylaminoethyl)ether, tin salts of organic carboxylic acids, and tin compounds such as dibutyltin dilaurate , as well as potassium salts such as potassium acetate. It is preferred that the further catalysts used are free of organotin compounds, in particular dibutyltin dilaurate.

The amount of these catalysts preferably used in the process of the present invention depends on the type of catalyst and is usually in the range of 0.01 pphp to 5 pphp (= parts by weight per 100 parts by weight of polyol). Used in amounts ranging from 0.1 pphp to 10 pphp.

The amount of water suitably present in the process of the invention depends on whether a physical blowing agent is used in addition to water. For foams blown with water only, the water content is usually preferably in the range of 1 pphp to 20 pphp, and if other blowing agents are used, the amount of water used is usually reduced to 0 or, for example, It reduces to the range of 0.1 pphp to 5 pphp. To obtain high foam densities, it is preferred not to use water or any other blowing agent.

Suitable physical blowing agents for the purposes of the present invention include gases such as liquefied CO ₂ and volatile liquids such as hydrocarbons having 4 or 5 carbon atoms, preferably cyclo-, iso- and n-pentane. - hydrofluorocarbons, preferably HFC245fa, HFC134a and HFC365mfc, also olefinic hydrofluorocarbons such as HHO1233zd and HHO1336mzzZ, hydrochlorofluorocarbons, preferably HCFC141b, oxygen-containing compounds such as methyl formate and dimethoxymethane, and hydrochlorocarbons, preferably include dichloromethane and 1,2-dichloroethane. Suitable blowing agents further include ketones (eg acetone) and aldehydes (eg methylal).

The stabilizers used may be the substances described in the prior art. Advantageously, the compositions of the invention contain one or more stabilizers. The stabilizer is in particular a silicon compound containing carbon atoms and is preferably selected from polysiloxanes, polydimethylsiloxanes, organo-modified polysiloxanes, polyether-modified polysiloxanes and polyether-polysiloxane copolymers.

Useful silicon compounds containing one or more carbon atoms include materials described in the prior art. It is preferred to use silicon compounds which are particularly suitable for particular types of foams. Suitable siloxanes are, for example, EP 0839852, EP 1544235, DE 102004001408, WO 2005/118668, US 2007/0072951, DE Patent application 2533074, EP 1537159, EP 533202, US 3,933,695, EP 0780414, DE 4239054, DE 4239054 References include published application No. 4229402 and EP 867465. Silicon compounds can be obtained as described in the prior art. Suitable examples are described, for example, in US Pat. No. 4,147,847, EP-A-0493836, and US Pat. No. 4,855,379.

Organically modified silicon compounds can especially be used. Particularly preferred useful organomodified silicon compounds include, for example, those conforming to formula (IV) below.
M _k D _m D' _n T _o Q _p (IV)
During the ceremony,
M = _[R2R12SiO1/ ^{2 ]} _,
^D = [ ^R1R1SiO2 _/2 ],
D′=[R ³ R ¹ SiO _2/2 ],
T = [ ^R1SiO3 _/2 ],
Q=[SiO4 _/2 ],
k = 0 to 22, preferably 2 to 10, more preferably 2,
m = 0 to 400, preferably 0 to 200, more preferably 2 to 100,
n = 0 to 50, preferably 0.5 to 20, more preferably 0.7 to 9,
o=0-10, preferably 0-5, especially 0,
p=0-10, preferably 0-5, especially 0,
^R2 is ^R1 or ^R3 ;
R ¹ is independently an alkyl group, an aryl group, or H, preferably methyl, ethyl, propyl, or phenyl, more preferably methyl or phenyl;
R ³ is an organic modification, such as a polyether, or a monovalent monovalent of 1 to 30 carbon atoms having at least one heteroatom selected from the group consisting of N, S, O, P, F, Cl, Br. part.
In formula (IV), R ³ is
_{-CH2CH2CH2O [ CH2CH2O} ^] _a ^[ _CH2CH ( _CH3 ) ^O ] _b [ _CHR4CHR4O ] _{cR5 ,
-CH2CH2CH2CN , _
-CH2CH2CF3 , _
-CH2CH2CH2Cl _ _}
It is preferably a portion selected from the group consisting of
During the ceremony,
R ⁵ is alkyl, aryl, urethane, carboxy, silyl, or H, preferably H, —Me, or —C(O)Me;
^R4 is optionally interrupted by oxygen, alkyl or aryl, more preferably H, Me, Et, or Ph;
a = 0 to 100, preferably 0.5 to 70, more preferably 1 to 40,
b = 0 to 100, preferably 0.5 to 70, more preferably 0 to 40,
c=0-50, preferably 0-15, especially 0,
a+b+c>3.

Unmodified silicon compounds can especially be used.
Particularly preferred useful unmodified silicon compounds include, for example, those conforming to formula (V) below.
_{MqDr (} V)
During the ceremony,
M and D are as defined in formula (IV) above;
q=2,
r=0-50, preferably 1-40, more preferably 2-30.

Particular preference is given to using the silicon compounds mentioned above, in particular the silicon compounds of the formulas (IV) and/or (V), individually or in combination with one another. In the case of mixtures, compatibilizers may also be used. This compatibilizer may be selected from the group consisting of aliphatic or aromatic hydrocarbons, preferably aliphatic polyethers or polyesters.

At least 10 equivalent percent (and up to 50 equivalent percent) of the ^R2 moieties of the siloxane compound of formula (IV) are alkyl of 8 to 22 carbon atoms (relative to the total number of R2 moieties of the siloxane compound) Advantageously, it is a group.

It is preferable to use 0.05 to 10 parts by mass of the silicon compound with respect to 100 parts by mass of the polyol component.

In particular, the use of the abovementioned silicon compounds in combination with the reaction products used according to the invention makes it possible to obtain very good results with respect to the polyurethanes sought by the invention.

In addition to or in place of water and any physical blowing agents, the additive composition of the present invention may contain other chemical blowing agents that generate gases and react with isocyanates, such as formic acid, carbamates, and carbonates. and so on.

Suitable flame retardants for the purposes of the present invention are preferably liquid organophosphorus compounds, for example halogen-free organophosphates such as triethyl phosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCPP ) and halogenated phosphates such as tris(2-chloroethyl) phosphate (TCEP) and organic phosphonates such as dimethyl methanephosphonate (DMMP), dimethyl propanephosphonate (DMPP), or solids such as These include ammonium polyphosphate (APP) and red phosphorus. Suitable flame retardants further include halogen compounds, such as halogenated polyols, and solids such as melamine and expandable graphite.

The process of the present invention particularly provides polyurethane systems, especially polyurethane foams, with good processability and low aldehyde emissions.

In the sense of the present invention, the term polyurethane is to be understood as a general term for any polymer obtained from di- or poly-isocyanates, polyols and other isocyanate-reactive species such as amines, for example urethanes. The bond need not be of the type in which it is the sole or primary bond. Polyisocyanurates and polyureas are also specifically included.

The production of the polyurethane system by the process of the invention, in particular the production of polyurethane foam by the process of the invention, and/or the production of the polyurethane system/polyurethane foam by any method known to those skilled in the art, for example by manual mixing. or preferably by using a high pressure or low pressure blower. The method of the invention can be carried out as a continuous operation or as a batch operation. Batch operations are preferred for methods of making molded foams, refrigerators, shoe soles, or panels. Continuous methods are preferred for methods of manufacturing insulation panels, metal composite elements, slabs or spray techniques.

In the process of the invention, it is preferred to mix the combination of the polyamine P used in the invention, especially the guanidine adduct, with the carrier material directly just before or during the reaction to form the urethane bonds. The combination is preferably mixed in a mix head and in a batch process for ready-made polyol systems. According to a preferred embodiment, the polyamine P, especially the guanidine adduct, can be dispersed directly in the silica or the polyamine P, especially the guanidine adduct, or silica, preferably solvent-dispersed silica, can be added to the polyol component. , can be added separately from each other.

The polyurethane system of the invention preferably comprises a total amount of carrier material and polyamine P of 0.001 wt % to 10 wt %, advantageously 0.01 wt % to 5 wt %, in particular of the total composition of the polyurethane system. It may contain 0.1 wt% to 3 wt%.

The polyurethane system of the invention is preferably a polyurethane foam, in particular for example rigid polyurethane foam, flexible polyurethane foam, viscoelastic foam, HR foam, semi-rigid polyurethane foam, thermoformable polyurethane foam or integral foam. Yes, preferably HR polyurethane foam.

The polyurethane systems, preferably polyurethane foams, of the present invention are, for example, refrigerator insulation, insulation panels, sandwich elements, pipe insulation, spray foams, 1- and 1.5-component can foams (1.5-component Can foam is foam produced by breaking a container in a can), imitation wood, modeling foam, packaging foam, mattresses, furniture cushioning, car seat cushioning, headrests, dashboards, car interiors products, automotive roof liners, sound absorbing materials, steering wheels, shoe soles, carpet backing foams, filter foams, sealing foams, sealants, and adhesives, binders or coatings for the manufacture of corresponding products. .

The present invention further provides a composition for making polyurethane foam, said composition comprising at least one urethane and/or isocyanurate catalyst, at least one blowing agent, at least one isocyanate component, and at least one and the additives included are a carrier material and one or more supporting compounds _comprising polyamine P, preferably polyamine P _; —CH ₂ —NH—(CH ₂ —CH ₂ —NH) _x —CH ₂ —CH ₂ —NH ₂ , where x is 0 to 4. , preferably 1 to 3, especially 1. For more details, reference is made to what has already been said in order to avoid duplication of description.

The term composition in this sense also includes multicomponent compositions, in which two or more components must be mixed in order to cause the chemical reaction to produce the polyurethane foam. must. The term composition in this sense includes, in particular, at least one urethane and/or isocyanurate catalyst, at least one blowing agent, at least one isocyanate component and at least one polyol component, as well as support material and polyamine P , in particular mixtures (mixtures) with guanidine reaction products.

Suitable polyurethane foam making compositions according to the present invention include a polyol in an amount such as from 25 wt% to 75 wt%, water in an amount such as from 1 wt% to 7 wt%, a catalyst in an amount such as from 0.05 wt% to 3 wt%, such as 0 wt%. Physical blowing agents in an amount of ˜25 wt % (eg 0.1 wt % to 25 wt %), stabilizers (eg silicon-containing and silicon-free stabilizers, especially silicon-containing and silicon-free in amounts of 0.3 wt % to 5 wt %). containing organic stabilizers as well as surfactants), for example isocyanate in an amount of 20-50 wt% and, for example, in an amount of 0.00001 wt% to 5 wt% (preferably 0.00005 wt% to 2.5 wt%) used in the present invention. and a polyamine P, especially a guanidine reaction product.

With respect to preferred embodiments of the compositions described above, in particular with respect to the carrier material and the polyamine P, in particular the guanidine reaction product, reference is made to the description above.

The present invention further provides an amount of preferably 0.001 wt% to 10 wt%, advantageously 0.01 wt% to 5 wt%, especially 0.1 wt% to 3 wt%, based on the total weight of the polyurethane system (especially polyurethane foam). , the total emissions of aldehydes from polyurethane systems (especially polyurethane foams), preferably from Emissions comprising formaldehyde, acetaldehyde, acrolein and aromatic aldehydes such as benzaldehyde, advantageously aldehyde emissions comprising formaldehyde, acetaldehyde, acrolein and benzaldehyde, in particular formaldehyde and acetaldehyde Provided is a method for reducing aldehyde emissions, said mixing may be carried out before and/or during the production of polyurethane systems (especially polyurethane foams).

The present invention further provides, as mentioned above, preferably 0.001 wt% to 10 wt%, advantageously 0.01 wt% to 5 wt%, especially 0.1 wt%, relative to the total weight of the polyurethane system (especially polyurethane foam). Provided is a polyurethane system (especially a polyurethane foam) comprising a carrier material and a polyamine P, in particular a guanidine reaction product, in an amount of ∼3 wt. obtained by mixing the carrier material and the polyamine P in the

The present invention further provides a support material and polyamine P, in particular polyamine P, for producing polyurethane foams with low emissions of aldehydes, preferably formaldehyde, acetaldehyde, acrolein and benzaldehyde, in particular low emissions of formaldehyde and acetaldehyde. The above uses of guanidine reaction products are provided.

In the examples given below, the invention is illustrated by way of example, but the invention and its scope of application, which is evident from the entire specification and the claims, are limited to the embodiments described in the examples. not a thing

Example

Preparation of silica dispersion:
To prepare the silica dispersion, the phase (silica) dispersed in a dispersing agent (e.g. glycol) is first filled into a container (e.g. a stainless steel beaker) and dissolved using a dissolution disk (diameter = 6 cm). Disperse at 5,000 rpm for 30 minutes. The use of a vacuum Dispermat addresses foam formation that can be caused by air ingress during the dispersing operation.

Production of HR Polyurethane Foam by High Pressure Foaming Machine

Foaming operations were performed using a Henneke HK 270 high pressure foamer equipped with an MQ mixing head. Specifically, the raw materials specified in Tables 1 and 2 were used to simulate a practically relevant cooling foam system. The amount of each reactant used is listed in Tables 3 and 4.

Using a mixing head, the pre-treated reaction mixture, together with a separating agent (Gorapur LK 8931-6 HW), was dosed into a box-shaped mold (dimensions 40 x 40 x 10 cm) heated to 55°C and then a box-shaped mold. The mold was sealed. The completed foam was demolded after 4 minutes. A wax-based release agent was applied using a spray gun to facilitate release.

The foamer was operated with the following parameters.
Polyol production corresponding to the sum of all components contained in the polyol formulation (see e.g. 107.2 g Form V1 in Table 3): 107.2 g/s, isocyanate production (index 75): 45.7 g/s Time: 6 seconds Mixing pressure: Polyol component 150 bar, isocyanate 160 bar
Raw material temperature in tank: Polyol 25°C, isocyanate 26°C

A standard force-to-crush test was performed on the foam immediately after demolding.

FORCE-TO-CRUSH measurement

The FORCE-TO-CRUSH measurement is a common method of measuring the open cell content of foams. In the production of automotive seat cushions, the open cell content of the foam is an important parameter to ensure the dimensional stability of the molding and prevent shrinkage after production.
The measurement was performed as follows.
Immediately after releasing the foam pad (<15 seconds later), place the pad in the starting position of the FTC tester. In the FTC tester, the measuring foot/measuring plate/measuring needle are positioned 115 mm away from the base plate, contact the foam, and move at a speed of 500 mm/min. The initial foam thickness is measured when the force reaches 5N. Without stopping at 5 N, the measuring foot further penetrates the foam at 500 mm/min until it reaches a position 50 mm away from the baseplate. At this point, FTC1 is measured. Carry out measurements without interruption. The measuring foot returns to the starting position (115 mm away from the bedplate) at 500 mm/min to complete the first cycle. Complete the same cycle as the first cycle 9 more times without delay. After the tenth cycle, the measuring paw stops at the starting position. The foam pad is then manually compressed sufficiently before being returned to the tester. A further cycle (11th cycle) is performed under the same conditions as the first 10 cycles. The foam thickness at the end of that cycle is then measured in the same manner as the foam thickness was measured at the beginning of the first cycle. The starting foam thickness is evaluated after FTC1, the remaining closed cell content is indicated by the difference between FTC10 and FTC11, and the compressibility of the foam is read from the shape of the curve (the degree of steep drop in FTC). FTC11 (the firmness of the new foam) can be used as a measure of foam cure.

Equipment parameters of the testing machine:
Universal testing machine H10K-S
Manufacturer: Tinius Olsen
Manufacturer number: 672
Maximum measurement: 10kN

Indentation hardness measurement according to DIN EN ISO 2439:2009-05 (ILD - indentation load, hardness at 40% compression)

Indentation hardness of elastomeric foams is one measure of foam stress properties. The above international standards define four methods (AD) for determining indentation hardness and one method (E) for determining compression set modulus and hysteresis loss of elastomeric foams. This time, method A is used. The definition of method A is as follows.

Method A—Determination of Indentation Hardness Index (40%/30 sec) Used for Individual Measurement of Indentation in Laboratory Tests

The force required to obtain a given indentation under the above conditions is measured. Measurements can be performed using the same equipment used for FTC measurements (see above).

Materials shall not be tested less than 72 hours after their manufacture. However, shorter aging times of 16 or 48 hours are also acceptable if the average results for these times can be demonstrated to differ less than ±10% from the value at 72 hours. It is permissible to conduct the test after either 16 or 48 hours of the prescribed time if the above criteria are met.

As described in ISO 23529, prior to testing, specimens must be conditioned without stress and tension in one of the following series of climatic conditions for at least 16 hours.
・(23±2)°C, relative humidity (50±5)%, or ・(27±2)°C, relative humidity (65±5)%

This adjustment period may be devoted to the final portion of the post-manufacture waiting time.

In the case of quality control, specimens may be taken as early as 12 hours after production and the test carried out after at least 6 hours of conditioning in one of a series of predetermined climatic conditions.

Place the test strip on the contact plate so that the center of the test strip or test area, where appropriate, lies directly under the center of the pushing ram. If the specimen has an indentation on one side, the side with the indentation faces the contact plate.

a) Apply a force of 5N to the selected test area and then measure the thickness of the specimen. Use that measurement as the zero indentation point.

b) The specimen is then indented at an indentation speed of (100±20) mm/min until an indentation of (70±2.5)% of its thickness is reached. As soon as this deformation occurs, the load is removed at the same speed.

c) Repeat this cycle of loading and unloading two more times.

Determination of indentation hardness index (40%/30 seconds)

Immediately after removing the load for the third time, the specimen is compressed by (40±1)% of its thickness.

Maintain this indentation for (30±1) seconds. At the end of this period, the force, expressed in Newtons, is measured, after which the load is removed from the specimen.

The formaldehyde and acetaldehyde contents of the molded foams produced by the method described above were corrected according to the VDA275 standard (VDA275 "Mouldings for the Automotive Interior-Determination of Formaldehyde Evolution"). Determination by bottle method, source: VDA 275, 07/1994, www.vda.de).

Principle of measurement

Specimens of specified mass and size were clamped above distilled water in a closed 1 L glass bottle and stored at constant temperature for the specified period of time in the above method. The bottles were then cooled and absorbed formaldehyde and acetaldehyde were measured in distilled water. The amounts of formaldehyde and acetaldehyde measured were divided by the dry weight of the extrudate (mg/kg).

Analytical Specimen: Sample Preparation, Sampling, and Sample Dimensions

After demolding, the foams were stored at 21° C. and about 50% relative humidity for 24 hours. Thereafter, samples of the molding were taken at suitable and representative points uniformly distributed across the width of the (cooled) molding. The foam was then wrapped in aluminum foil and sealed in a polyethylene bag.

The size of the samples was 100 x 40 x 40 mm each (approximately 9 g). Three samples per molding were taken for aldehyde testing.

Test Procedure: Formaldehyde/Acetaldehyde Release

The encapsulated samples were measured directly immediately after being obtained. Prior to analysis, samples were weighed using an analytical balance to an accuracy of 0.001 g. A quantity of 50 ml of distilled water was pipetted into each vial used. The sample was put into a glass bottle, the container was sealed, and stored at a constant temperature of 60° C. for 3 hours in a heat-retaining cabinet. At the end of the test period, the container was removed from the warming cabinet. After standing at room temperature for 60 minutes, the sample was removed from the test bottle. It was then derivatized by the DNPH method (dinitrophenylhydrazine). At that time, 900 μl of aqueous phase were mixed with 100 μl of DNPH solution. A DNPH solution was prepared as follows. 50 mg of DNPH in 40 mL of MeCN (acetonitrile) was acidified with 250 μL of dilute HCl (1:10) and made up to 50 mL with MeCN. After derivatization, samples were analyzed using HPLC (High Performance Liquid Chromatography). Separation into individual aldehyde homologues was performed.

HPLC Instrument Parameters The following instruments were used for analysis.
Agilent Technologies 1260
Chromatographic column: Phenomenex Luna250 ^* 4.6mm C18, particle size 5μ
Mobile Phase: Water Acetonitrile Gradient Detection: UV365nm

Ingredient amounts are expressed in grams.

Foaming results showed that the addition of additive 1 produced a positive change in formaldehyde emissions (V2) compared to zero foam without additive (V1), but closed cell content (FTC) and ILD hardness shows a further significant decrease in . The difference between the FTC1 values of V1 and V2 is almost 20%, which can be judged as a significant reduction in closed cell content, thus having a significant impact on the processability of the formulation.

When Additive 2 (EM1) is additionally added to Additive 1 (separately added), a positive effect is found in the form of a significant reduction in the emissions of formaldehyde generated, which is close to the limit of detection. Furthermore, the closed cell content (FTC 1-10, 11) and ILD hardness can be increased almost to the starting value. The same result is obtained if Additive 1 and Additive 2 are pre-mixed in the same mixing ratio and then added (EM2).

Example EM3 is the same mixture as EM2, but with a lower proportion of carrier material. The degree of improvement in properties observed here is of the same order. Example EM4 as an Aerosil dispersion dispersed directly in the guanidine reaction product (without any additional dispersant, as the guanidine reaction product is functioning as such here) is similarly relatively good. bring good results.

Foaming results show that with the addition according to the invention of carrier materials and polyamine P it is possible to produce PU foams with reduced formaldehyde emissions, improving the ILD hardness and processability reflected in the closed cell content (FTC). level can be maintained.

Ingredient amounts are expressed in grams.

Foaming results showed that the addition of additive A produced a positive change in formaldehyde emissions (V4) compared to zero foam without additive (V3), but closed cell content (FTC) was even more significant. , and in this case, being so low, indicates that the ILD hardness was also significantly reduced. The difference between the FTC1 values of V3 and V4 is even more than 30%, which is judged as a significant reduction in closed cell content and therefore has a significant impact on the processability of the formulations.

If, instead of additive A, additive B (EM5) according to the invention is added (already fully dispersed variant), good effects are found in foams with reduced formaldehyde emissions, although here In particular, good effects are found on the improvement of the closed cell content (FTC 1-10, 11) and the ILD hardness which is almost back to the starting value.

The foaming results show that the addition according to the invention of carrier materials and polyamine P makes it possible to produce PU foams with reduced formaldehyde emissions, improving the ILD hardness and processability as reflected in the closed cell content (FTC) at the start. level can be maintained.

Claims (8)

polyurethane system by reacting at least one polyol component with at least one isocyanate component in the presence of one or more catalysts for at least one of isocyanate-polyol, isocyanate-water reaction, and isocyanate trimerization. A method of making, wherein the reaction is carried out in the presence of synthetic silica and polyamine P,
The polyamine P results from the reaction of a guanidine salt with a polyamine of formula (I),
_H2N - _CH2 -CH2 _- NH-(CH2 _- CH2 _- NH) _x - _CH2 - _CH2 - _NH2 (I)
wherein x = 0 to 4,
A method, wherein said reaction of said guanidine salt and said polyamine is carried out at a molar ratio of guanidine salt to polyamine ranging from 5:1 to 1:5. 2. Process according to claim 1, characterized in that the synthetic silica used is fumed silica or precipitated silica. The polyamine P used has the formula (II)
H[—(HN—CH ₂ —CH ₂ ) _a —NH—C(=NHR ⁺ X ⁻ )] _c —NH—(CH ₂ —CH ₂ —NH—) _b H (II)
A compound represented by
Said compound is obtained by reacting a guanidine salt with a compound represented by formula (I),
During the ceremony,
a is independently 0 to 6;
b is independently 0 to 6;
c is independently 1 to 4;
R is H or (CH ₂ —CH ₂ —NH—)d _H ;
d is independently 0-6;
if d>0 and R is not H, a and b may each be 0; if a>0, d and b may each be 0; or if b>0 , d and a may each be 0,
A method according to claim 1, characterized in that X ^- is an anion. The method according to any one of claims 1 to 3 , wherein the synthetic silica and the polyamine P are used in a total mass fraction of 0.01 to 10 parts with respect to 100 parts of the polyol component. . (i) or (ii) below;
(i) separately adding the polyamine P and the synthetic silica to the reaction mixture used to prepare the polyurethane system, the synthetic silica being dispersed in a liquid ;
(ii) mixing said polyamine P and said synthetic silica prior to addition to the reaction mixture used to prepare said polyurethane system ;
5. A method according to any one of claims 1 to 4, characterized in that . 6. Process according to any one of claims 1 to 5 , characterized in that the polyurethane system produced is a polyurethane foam. 7. The method of claim 6 , comprising 0.001 wt% to 10 wt% synthetic silica and polyamine P in the polyurethane system . 3. Process according to claim 1 or 2 , characterized in that the polyurethane system is a rigid polyurethane foam, a flexible polyurethane foam or a semi-rigid polyurethane foam .